Bacteriostatic toilet bowl cleaner compositions

ABSTRACT

New automatic toilet bowl cleaner compositions that are capable of inhibiting the growth or multiplication of microbiological organisms are described herein. The bacteriostatic agent in the above compositions is 5-chloro-2-(2,4-dichlorophenoxy)phenol.

United States Patent [1 1 Carmello et al.

[451 July 29,1975

[ BACTERIOSTATIC TOILET BOWL CLEANER COMPOSITIONS [75] Inventors: Robert Carmello, Dumont; Barry A.

Salka, Clifton; Garland G. Corey, Milltown, all of NJ.

[73] Assignee: American Home Products Corporation, New York, N.Y.

22 Filed: Dec. 6, 1972 211 App]. No.: 312,767

3,650,964 3/1972 Sedliar et a1 252/106 3,700,601 10/1972 Bloching 252/106 X 3,721,629 3/1973 Goodenough 252/106 X 3,738,943 6/1973 Kancko 252/106 X 3,762,875 10/1973 Burmeister 252/106 X OTHER PUBLICATIONS lrgasar DP300," 15 pages, CIBA-GEIGY Greensboro, N.C.

Primary Examiner-Benjamin R. Padgett Assistant ExaminerE. A. Miller Attorney, Agent, or FirmStephen Venetianer [57] ABSTRACT New automatic toilet bowl cleaner compositions that are capable of inhibiting the growth or multiplication of microbiological organisms are described herein. The bacteriostatic agent in the above compositions is 5-chloro-2-(2,4-dich1orophenoxy)phenol.

10 Claims, No Drawings BACTERIOSTATIC TOILET BOWL CLEANER COMPOSITIONS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to novel toilet bowl cleaner compositions. These compositions possess antimicrobial properties at the extremely low dilutions which are normally encountered with a product of this nature.

2. Description of the Prior Art Compositions which automatically dispense cleaning agents and cleaning adjuncts into toilet bowls have been in commercial use for many years. However, the inhibition of the growth or multiplication of microbiological organisms in products of the above nature has been difficult to accomplish. This difficulty is due to the fact that most antimicrobial agents are ineffective at the extreme'dilutions that automatic bowl cleaners are used. I

Recently, a new antimicrobial agent, namely 5- chloro-2-(2,4-dichlorophenoxy)phenol has been disclosed in US. Pat. No. 3,506,720. The assignee of this patent (Ciba-Geigy) has published data (lrgasa n DP- 300, Publication DC-25) which indicates that the mini-- mum inhibitory concentration of 5-chloro-2-( 2,4- dichlorophenoxy)phenol required for specific microorganisms is lppm for S. aureus and P. mirabilis and 3ppm for E. coli.

SUMMARY OF THE INVENTION DESCRIPTION OF SPECIFIC EMBODIMENTS The novel liquid composition of this invention comprises:

Ingrcdient By Weight Isopropanol 10-20 5-chloro-2-( 2,4-dichlorophenoxy )phenol 0.5-6 Alkoxylated primary fatty alcohol 0.1-20 Linear Alkyl Aryl Sulfonate Salt I 05-20 Sodium hydroxide -2 Water, Dye, Perfume Sufficient to make up to 100% The preferred formula for an effective liquid cleaning and bacteriostatic composition is as follows:

Ingredient By Weight- Isopropanol 14-16 -chloro-2-( 2.4-dichlorophenoxy)phenol l.l-l .6 Alkoxylated primary fatty alcohol 4-17 Linear Alkyl Aryl Sulfonate Salt 0.5- Water, Dye, Perfume Sufficient to make up to 100% Sodium sulfate; Perfume, Dye

Sodium sulfate, Perfume, Dye Sufficient to make up to The preferred formula foran effective solid cleaning and bacteriostatic composition is as follows:

Ingredients -By-Weight 5-chloro-2-(2,4-dichlorophenoxy)phenol l-3 (97%-minimum activity) Alkoxylated primary fatty alcohol I 2-8 Ethoxylated alcohol adduct 25-35 Polyethylene glycol 2-8 Sufficient to make up to 100% Examples of alkoxylated primary alcohols that are useful in this itivention are those alkoxylated primary alcohols wherein the alkyl chain length is primarily nw Examples of linear alkyl aryl sulfonate salts that are useful in this invention are the salts of an alk'ylaryl sulfonate wherein the alkyl carbon chain length is C -C The novel composition in its solid form contains an ethoxylated alcohol adduct whose primary alcohol chain length is about C, C In addition to the cleaning and bacteriostatic properties that the novel formulations of this invention possess, they also have the ability to reduce the surface tension of water.

As will be illustrated in the following examples, the liquid compositions of this invention have the'ability to exhibit bacteriostatic properties at use levels as low as 0.2 parts per million of the anti-microbial. Thesolid compositions exhibit bacteriostatic properties at use levels as low as 0.1 parts per million of the antimicrobial. The examples will also indicate the antimicrobial agents known in the prior art are either ineffective or are not readily or efficiently compounded or solubilized.

The following examples illustrate the above described invention. The bacteria employed as the test organisms are representative of both gram negative and gram positive'bacteria. The test procedure employed is the Agar Plate Test and the Agar Cup Plate Test as described in U.S.D.A.circular No'. 198, 1931. The results are reported as zones of inhibition and measured in millimeters.

EXAMPLE 1 Sufiicient to make Water, Dye, Perfume :up to I007! 3 4 Average Zone of Inhibition (mm) Dilution l:23,000 -Continued Ingredient By Weight T070 propylene oxide S. aureus [5. col! P. mirabllis of a near alcohol whose carbon chain length is C ,-C Agar P Plate Test 10 5 3 5 Water, Dye. Perfume Sufficient to Agar Plate Test 5 2 1 make up to A preferred alternate formulation is represented by Example 2. I

Average Zone of Inhibition (mm) Dilution l:23,000

EXAMPLE 2 S. aureus E. culi Ingredient By weight Agar Cup Plate Test 2.5 0

lsopi'opanol (99%;) 15.00 qg fi ap y)P The above is an example of the use of another antimia minimum ac vi y Triethanolaminedodecylbenzensulfonate (40%) 15.00 crobla! agent emPloyed at a h hlgher level h Water, Dye, Perfume Surficient to those in the previous examples which was ineffective make up to 100% against E. coli.

EXAMPLE 5 Ingredient By Weight Average Zone of Inhibition(mm) Dilution 1:23,000

- 4,5 Dibromosalicylanilicle and 3,45, Tribromosalicylanilide (1:1 mixture) 6.00 S. aureus E. coli P. mirabilis g fi Glycol (molecular weight 50.00 Octyl phenoxypoly (ethyleneoxy) Ethanol 30.00 Agar P Plate Test 7 3 3 Water Sufficient to Agar Plate Test 6 3 3 make up to EXAMPLE 3 Average Zone of Inhibition (mm) Dilution l:20,000

Ingredient By Weight lsopmpanol (99%) I500 Agar Cup Plate Test 16 l l 5-chl0r0-2-( 2,4-dichlorophenoxy )phenol 1.50 40 (97% minimum activity) Triethanolaminedodecylberizensulfonate (40%) 11.25 The above is an example of the use of a different anti 50% ethylene oxide 4.50 10% propylene oxid adduct microbial agent which requires high levels of solubiliza near wiwse ers and which was used at higher levels itself to achieve carbon chain length is C C b t 1 l Water, Dye, Perfume Sufficient to ac eno oglca ac ymake up to EXAMPLE 6 Ingredient By Weight Average Zone of Inhibition (mm) Dilution l:23,000 3,4'5 Tribromosalicylanilide 6.00 Polyethylene Glycol (molecular weight 60.00 about 200) S. aureus E. coli P. mirabilis g i f (ethyleneoxy) ethanol Agar Cup Plate Test 7 15 2.5

Average Zone of Inhibition (mm) Dilution l:20,000

EXAMPLE 4 S. aureus E. coli Agar Cup Plate Test 10 4 Ingredient By Weight (Partial) Isopropanol (99%) C 7 C d 450 l 3 7 5 g fifgflf gg g g flg i ffi 5,00 This example illustrates another antimicrobial agent n-Alkyl (68% 12. 32 i y 5 00 which requires high levels of solubilizers and which re- Ethylbenzyl Ammomum chlonde sults in only a partial zone of inhibition at the high level 50% ethylene oxide l0)? propylene oxide uddlict employed.

EXAMPLE 7 Ingredient Ey Weight Alkyl pyridinium 5-chloro-2-mercapto- 3 12.00 benzothiazole (96%) N-methgl-Z-pyrrolidone 60.00 Octyl p enoxy poly (ethyleneoxy) ethanol 10.00 Water 18.00

Average Zone of Inhibition (mm) Dilution 1:20.000

S. aureus I, E. coli AsarCupPlaG st I 7 1 '0 This example illustrates yet *another antimicrobial agent which though used at a higher level-does not result in a zone of inhibition on E. 0011' I 6 EXAMPLE 8 This example illustrates the use of the solid formulation of this invention as a toilet bowl-cleaneL'The use dilution for microbiological activityw'ith this: composition is 0.30 parts per million of the formulationper 23,000 parts of water. I

Component By Weight 100 moles of ethylene oxide adduct of 31.00

a primary alcohol whose carbon length y c is ut- 20 Q Polyethylene Glycol (molecular 3 weight about 6,000) 1 y 50% ethylene oxide 10% propylene oxide of a linear alcohol whose carbon chain length is C C I S-chloro-2-(2,4-dichlorophenoxy)phenol 1.25 (97% minimum activity) Sodium Sulfate 55.25

' Sufficient to make up to 100% Perfume, Dye

Average Zone of Inhibition (mm) I S. aureus coli P. mirabilis Agar Cup Plate Test 4.5 7' v 2 Q I w v 2.5

EXAMPLE 9 This Example illustrates the use of -chloro-2-(2,4- dichlorophenoxy)phenol in the following liquid formulation where it is present at 0.50% by weight in a use dilution of 1:23,000 and 1:40.000.

Ingredients By Weight lsopropanol (99%) 15.00 5-chloro-2-( 2,4-dichlorophenoxy )phenol 0.50 (97% minimum activity) 50% ethylene oxide dd 12.00 10% propylene oxide a um of a linear alcohol -whose carbon chain length is C -C Water 67.75 Sodium Xylene Sulfonate (40%) 2.50

-Continued Ingredients By Weight Dye l .00 Perfume 1 .25

Average Zone of Inhibition (mm) Perfume, Dye

, make up to Average Zonefof Inhibition (mm) S. aureus E. coli P. mirabilis Agar Cup Plate Test 2.5 0 0 This example illustrates the use of an antimicrobial agent which does not exhibit activity in the composition.

EXAMPLE 1 1 Component By Weight Ethoxylated Alcohol Adduct 31.00 Polyethylene Glycol (mol. wt. about 6000) 5.00 Oxyethylated Alcohol Surfactant 5.00- 3,4',5 Tribromosalicylanilide 2.50 Sodium Sulfate 54.00

Perfume, Dye Sufficient to make up to 100% Average Zone of Inhibition (mm) S. aureus E. coli P. mirabilis Agar Cup Plate Test 0 0 0 This example illustrates a total lack of activity of an antimicrobial in the composition.

EXAMPLE 1 2 The following data represents the ability of the preferred compositions of this invention to help retard stain buildup on a ceramic surface immersed in a solution containing an iron salt. Results are reported as units of stain pickup on white ceramic tiles. Less than 1 unit difference is visible to the-naked eye.

Surface Average Units Tension lron Stain Pickup Dynes/CM Composition (Example 1) 4.1 41.4 Water 5.8 72 Composition (Example 8) 2.5 33 Water 6.1 72

We claim:

1. A method for preventing the growth ormultiplication of E. Coli in toilet bowls which comprises dispensing into the water of a toilet an antibacterial liquid composition consisting essentially of:

Ingredient By Weight lsopropanol 10-20 S-chloro-Z-(2,4-dichlorophenoxy)phenol 0.5-6 Alkoxylated primary fatty alcohol 0.1-20 Linear alkyl aryl sulfonate salt 0.5-20 Sodium hydroxide -2 Water. dye, perfume Sufficient to wherein -chloro-2(2,4-dichlorophenoxy)phenol is present at a use dilution level in amounts of about 0.2 parts per million to less than 3.0 parts per million and wherein the alkyl chain length of the alkoxylated primary alcohol is from about 12 carbon atoms to about 18 carbon atoms.

2. An antibacterial liquid composition consisting essentially of:

Ingredient By Weight lsopropanol I 1 14-16 5-chloro-2-( 2,4-dichlorophenoxy )phenol 0.5-1.6 Alkoxylated primary fatty alcohol 4-17 Linear alkyl aryl sulfonate salt 0.5-l0.0 Sodium hydroxide 0-2 Water, dye,- perfume Sufficient to make up to .0

wherein 5-chloro-2-(2,4-dichlorophenoxy)phenol is present at a use dilution level in amounts of about 0.2 parts per million to less than 0.7 parts per million and wherein the alkyl chain length of the alkoxylated primary alcohol is from about 12 carbon atoms to about 18 carbon atoms.

3. A composition according to claim 2, wherein the linear alkyl aryl sulfonate salts have alkyl carbon chain length from C -C ,4. A' compo sition accordin to claim 2 wherein the 'alkoxylated'primary fatty'alcoholis a 50% ethylene oxide, 10% propylene oxideadduct of a linear alcohol whosecarbon chain length is C -C 5.

5. A composition according toblaim 3 wherein the alkyl "aryl sulfonatesaltis sodium xylene sulfonate.

6. A composition according to claim 3 wherein the alkyl aryl sulfonate salt is tri-ethanolaminedodecylbenzenesulfonate. '4'. a m"- 7. A method for preventing the growth or multiplication of S. Aureus,., P.-Mirabilis and E. Coli in toilet bowls ,which comprises dispensing the composition of claim 2 into the water of a toilet to prevent such growth. 8'. A composition according to claim 2 wherein 5- chloro-2-(2,4-dichlorophenoxy)phenol has a lower limit'ofabout l.'l"pe'rcent;v P 1 9. An antibacterialliq'uid composition consisting essentially of:

nsrc i m m. "t By Weight Alkoxylated primary fatty alcohol v v 4.1 7

Water, dye, perfume :Sufficientito make up to 100% Ingredient I By Weight lsopropanol 14-16 5-chloro-2-( 2,4-dichlorophenoxy )phenol 0.5- l .6

Linear alkyl aryl sulfonate salt 0.5-10.0

Sodium hydroxide; 0-2

Water, dye, perfume Sufficient to make up to wherein 5-chloro-2-(2,4-dichlorophenoxy)phenol is present me use dilution level in amounts of about 0.2

parts per million to less than 0.7 parts per million. 

1. A METHOD FOR PREVENTING THE GROWTH OR MULTIPLICATION OF E. COLI IN TOILET BOWLS WHICH COMPRISES DISPENSING INTO THE WATER OF A TOILET AN ANTIBACTERIAL LIQUID COMPOSITION CONSISTING ESSENTIALLY OF:
 2. An antibacterial liquid composition consisting essentially of:
 3. A composition according to claim 2, wherein the linear alkyl aryl sulfonate salts have alkyl carbon chain length from C1-C15.
 4. A composition according to claim 2 wherein the alkoxylated primary fatty alcohol is a 50% ethylene oxide, 10% propylene oxide adduct of a linear alcohol whose carbon chain length is C12-C15.
 5. A composition according to claim 3 wherein the alkyl aryl sulfonate salt is sodium xylene sulfonate.
 6. A composition according to claim 3 wherein the alkyl aryl sulfonate salt is tri-ethanolaminedodecylbenzenesulfonate.
 7. A method for preventing the growth or multiplication of S. Aureus, P. Mirabilis and E. Coli in toilet bowls which comprises dispensing the composition of claim 2 into the water of a toilet to prevent such growth.
 8. A composition according to claim 2 wherein 5-chloro-2-(2,4-dichlorophenoxy)phenol has a lower limit of about 1.1 percent.
 9. An antibacterial liquid composition consisting essentially of:
 10. An antibacterial liquid composition consisting essentially of: 